CN109638279A - A kind of preparation method of nickelic ternary material and products thereof and application - Google Patents
A kind of preparation method of nickelic ternary material and products thereof and application Download PDFInfo
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- CN109638279A CN109638279A CN201811624977.5A CN201811624977A CN109638279A CN 109638279 A CN109638279 A CN 109638279A CN 201811624977 A CN201811624977 A CN 201811624977A CN 109638279 A CN109638279 A CN 109638279A
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- ternary material
- nickelic ternary
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention proposes that method of modifying of a kind of nickelic ternary material and products thereof and application, the nickelic ternary material general formula are LiNixCoyMnzO2, wherein x+y+z=1, y≤0.1,0.6 < x≤0.8 prepare nickelic ternary material precursor, in BF first3Under atmosphere, pre-burning is carried out to nickelic ternary material precursor, it is modified to its surface pre-burning, excessive lithium source is then added and carries out high-temperature calcination, to obtain the nickelic ternary material of surface-stable type.The features such as entirely modified nickelic ternary material preparation method is simply controllable, and the modified nickelic ternary material of preparation has that first effect is high, SEI film even compact, and gram volume is big, good cycle.
Description
Technical field
The invention belongs to material chemistry technical fields, and in particular to the preparation method and its production of a kind of nickelic ternary material
Product and application are applied to lithium ion battery.
Background technique
With the high speed development of lithium ion battery, and under the guidance energetically of policy, high capacity lithium ion battery becomes
The hot spot of people's research, and the performance of positive electrode plays conclusive effect to the chemical property of lithium ion battery, therefore,
The research and development of anode material for lithium-ion batteries are particularly important.Although commercial cobalt acid lithium energy density is relatively high at present,
But its own it is some be difficult to the shortcomings that evading, as cost, a large amount of of Co use and poor circulation limits cobalt acid lithium
Sustainable development.
The tertiary cathode material of substituted cobalt acid lithium status, general formula LiNi1-x-yCoxMnyO2, common proportion has 111,
Since 424,523,622,811,2018 years, as public subsidies policy is directly linked up with battery energy density, ternary battery is special
It is not that the development of nickelic 811 battery of high-energy density receives the favor of many producers.Meanwhile along with the height of cobalt price
Rise, nickelic 811 become the development trend of power battery.
Meanwhile nickelic ternary material is also faced with a series of intractable challenges: 1. losses of oxygen and not in the energized state
Reversible structure transformation.2.Ni2+And Li+It is high to mix nickel content.3. micro-crack is during long circulating, performance degradation.4. surface
Basicity is high, to CO2And H2O is sensitive.
For this purpose, the preparation method modified present inventors studied nickelic positive electrode, the method for modifying is easy to operate, technique
Simply, it is suitable for industrialized production, is applied in nickelic ternary material, has that first effect is high, SEI film even compact, gram volume is big,
The features such as good cycle.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of that present invention to provide a kind of preparation methods of nickelic ternary material.
Another object of the present invention is: providing a kind of nickelic ternary material product of above method preparation.
Another object of the present invention is to: a kind of application of the said goods is provided.
The object of the invention is realized by following proposal: a kind of preparation method of nickelic ternary material, the nickelic ternary material
Material chemical formula is LiNixCoyMnzO2, wherein x+y+z=1, the .8 of y≤0.1,0 .6 < x≤0 prepare nickelic ternary material forerunner
Body, in BF3Under atmosphere, pre-burning is carried out to nickelic ternary material precursor, it is modified to its surface pre-burning, excessive lithium is then added
Source carries out high-temperature calcination and includes the following steps: to obtain the nickelic ternary material of surface-stable type
(1) coprecipitation is used, configures nickel source compound, cobalt source compound, manganese source compound to by the molar ratio of 8:1:1
Nickel cobalt manganese source chemical combination is added in carbonate aqueous solution by the aqueous solution of 1mol/L, the aqueous solution that carbonate is separately configured as 1mol/L
In object mixed aqueous solution, then precursor pulp is filtered, washing, it is dry in vacuum oven, obtain MCO3Precursor
End, wherein M is Ni, Co, Mn；
(2) by MCO3Precursor powder is placed in tube furnace, under inert atmosphere, 5 DEG C/min of heating rate,
Temperature is controlled at 300~400 DEG C, after heat preservation 2 hours, is passed through BF3Gas continues natural cooling after heat preservation 4~6 hours,
Then powder is taken out；
(3) finally, carrying out high-temperature calcination after the excessive lithium source of modified powder addition is sufficiently mixed, obtaining nickelic ternary just
Pole material.
Wherein, step (1) the nickel source compound, cobalt source compound, manganese source compound be respectively nickel acetate, cobalt acetate,
Manganese acetate.
Step (2) inert atmosphere is nitrogen or argon gas.
On the basis of above scheme, step is passed through BF described in (2)3Gas is to stop being passed through nitrogen or argon gas, will be managed
Formula furnace flowing gas is changed to BF3Gas, the temperature control is at 350~360 DEG C.
The excessive lithium source of addition described in step (3) is MCO3The molar ratio of precursor powder and lithium carbonate is C (Li): C
(Ni+Co+Mn) 1 .05 of >.
The present invention provides a kind of nickelic ternary material, is prepared according to any of the above-described the method.
The present invention provides a kind of nickelic ternary material in lithium ion battery as the application of positive electrode.
The invention proposes a kind of preparation methods that nickelic positive electrode is modified, and the method for modifying is easy to operate, technique letter
It is single, it is suitable for industrialized production, is applied in nickelic ternary material, there is head to imitate high, SEI film even compact, gram volume is big, follows
The features such as ring performance is good.
Detailed description of the invention
Fig. 1 is the nickelic ternary material SEM of embodiment 1 figure；
Fig. 2 is the nickelic ternary material charge and discharge electrograph of embodiment 1.
Specific embodiment
The present invention is described in detail by following specific example, but protection scope of the present invention is not only restricted to these
Examples of implementation.
Embodiment 1:
A kind of nickelic ternary material, the nickelic ternary material chemical formula are LiNixCoyMnzO2, wherein x+y+z=1, y≤0.1,
The .8 of 0 .6 < x≤0, prepares nickelic ternary material precursor, in BF3Under atmosphere, pre-burning is carried out to nickelic ternary material precursor,
It is modified to its surface pre-burning, excessive lithium source is then added and carries out high-temperature calcination, to obtain the nickelic ternary material of surface-stable type
Material, prepares as follows:
Nickel acetate, cobalt acetate, the material that manganese acetate molar ratio is 8:1:1 are weighed respectively, are dissolved in 500ml deionized water, are matched
It is set to the aqueous solution of 1mol/L, carbonate is separately configured the aqueous solution that 500ml is 1mol/L, then carbonate aqueous solution is added
In nickel cobalt manganese source compound mixed aqueous solution, then precursor pulp is filtered, washing, it is dry in vacuum oven, it obtains
MCO3Precursor powder；
Then by MCO3Precursor powder is placed in tube furnace, and under nitrogen atmosphere, 5 DEG C/min of heating rate, temperature control exists
After 350 DEG C, heat preservation 2 hours, BF is passed through after closing nitrogen3Gas continues natural cooling after heat preservation 5 hours, then takes powder
Out；
Finally, carrying out high-temperature calcination after the excessive lithium source of modified powder addition is sufficiently mixed, obtaining nickelic tertiary cathode material
Material.
By the nickelic tertiary cathode material of product mix a certain proportion of binder (PVDF, 10 wt%) and conductive agent (SP, 10
Wt%), it is prepared into button half-cell after coating, stands 24 h after being assembled into battery.Under conditions of environment temperature is 25 DEG C, make
Charge-discharge test is carried out with new Weir battery test system.Fig. 1 is that the SEM of modified nickelic ternary material schemes, and Fig. 2 is nickelic three
The charge and discharge electrograph of first material, charge-discharge magnification are 0.1C.Wherein, formation voltage 3.0-4.3V, formation efficiency 84.49%, chemical conversion
Step: charging 0.05C mono- hour, 0.05C is charged to 3.4V, then 0.1C to 4.3V, and discharge 0.1C to 3.0V.
Embodiment 2:
A kind of nickelic ternary material, it is identical as embodiment step, it prepares as follows:
Nickel acetate, cobalt acetate, the material that manganese acetate molar ratio is 8:1:1 are weighed respectively, are dissolved in 500ml deionized water, are matched
It is set to the aqueous solution of 1mol/L, carbonate is separately configured the aqueous solution that 500ml is 1mol/L, then carbonate aqueous solution is added
In nickel cobalt manganese source compound mixed aqueous solution, then precursor pulp is filtered, washing, it is dry in vacuum oven, it obtains
MCO3Precursor powder；
Then by MCO3Precursor powder is placed in tube furnace, and under nitrogen atmosphere, 5 DEG C/min of heating rate, temperature control exists
After 360 DEG C, heat preservation 2 hours, BF is passed through after closing nitrogen3Gas continues natural cooling after heat preservation 5 hours, then takes powder
Out；
Finally, carrying out high-temperature calcination after the excessive lithium source of modified powder addition is sufficiently mixed, obtaining nickelic tertiary cathode material
Material.
By the nickelic tertiary cathode material of product mix a certain proportion of binder (PVDF, 10 wt%) and conductive agent (SP, 10
Wt%), it is prepared into button half-cell after coating, stands 24 h after being assembled into battery.Under conditions of environment temperature is 25 DEG C, make
Charge-discharge test is carried out with new Weir battery test system.
Embodiment 3:
A kind of nickelic ternary material, it is identical as embodiment step, it prepares as follows:
Nickel acetate, cobalt acetate, the material that manganese acetate molar ratio is 8:1:1 are weighed respectively, are dissolved in 500ml deionized water, are matched
It is set to the aqueous solution of 1mol/L, carbonate is separately configured the aqueous solution that 500ml is 1mol/L, then carbonate aqueous solution is added
In nickel cobalt manganese source compound mixed aqueous solution, then precursor pulp is filtered, washing, it is dry in vacuum oven, it obtains
MCO3Precursor powder；
Then by MCO3Precursor powder is placed in tube furnace, and under nitrogen atmosphere, 5 DEG C/min of heating rate, temperature control exists
After 300 DEG C, heat preservation 2 hours, BF is passed through after closing nitrogen3Gas continues natural cooling after heat preservation 5 hours, then takes powder
Out；
Finally, carrying out high-temperature calcination after the excessive lithium source of modified powder addition is sufficiently mixed, obtaining nickelic tertiary cathode material
Material.
By the nickelic tertiary cathode material of product mix a certain proportion of binder (PVDF, 10 wt%) and conductive agent (SP, 10
Wt%), it is prepared into button half-cell after coating, stands 24 h after being assembled into battery.Under conditions of environment temperature is 25 DEG C, make
Charge-discharge test is carried out with new Weir battery test system.
Claims (7)
1. a kind of preparation method of nickelic ternary material, the nickelic ternary material chemical formula is LiNixCoyMnzO2, wherein x+y+
The .8 of z=1, y≤0.1,0 .6 < x≤0, which is characterized in that nickelic ternary material precursor is prepared, in BF3Under atmosphere, to nickelic
Ternary material precursor carries out pre-burning, modified to its surface pre-burning, and excessive lithium source is then added and carries out high-temperature calcination, to obtain
The nickelic ternary material of surface-stable type is obtained, is included the following steps:
(1) coprecipitation is used, configures nickel source compound, cobalt source compound, manganese source compound to by the molar ratio of 8:1:1
Nickel cobalt manganese source chemical combination is added in carbonate aqueous solution by the aqueous solution of 1mol/L, the aqueous solution that carbonate is separately configured as 1mol/L
In object mixed aqueous solution, then precursor pulp is filtered, washing, it is dry in vacuum oven, obtain MCO3Precursor
End, wherein M is Ni, Co, Mn；
(2) by MCO3Precursor powder is placed in tube furnace, under inert atmosphere, 5 DEG C/min of heating rate,
Temperature is controlled at 300~400 DEG C, after heat preservation 2 hours, is passed through BF3Gas continues natural cooling after heat preservation 4~6 hours, so
Powder is taken out afterwards；
(3) finally, carrying out high-temperature calcination after the excessive lithium source of modified powder addition is sufficiently mixed, obtaining nickelic ternary just
Pole material.
2. the preparation method of nickelic ternary material according to claim 1, which is characterized in that step (1) the nickel source chemical combination
Object, cobalt source compound, manganese source compound are respectively nickel acetate, cobalt acetate, manganese acetate.
3. the preparation method of nickelic ternary material according to claim 1, which is characterized in that step (2) described inert atmosphere
For nitrogen or argon gas.
4. according to claim 1 or the preparation method of the 3 nickelic ternary materials, which is characterized in that described logical in step (2)
Enter BF3Gas is to stop being passed through nitrogen or argon gas, and tube furnace flowing gas is changed to BF3Gas, the temperature control exist
350~360 DEG C.
5. the preparation method of nickelic ternary material according to claim 1, which is characterized in that step was added described in (3)
Amount lithium source is MCO3The molar ratio of precursor powder and lithium carbonate is C (Li): C (Ni+Co+Mn) > 1.05.
6. a kind of nickelic ternary material, it is characterised in that -5 any the methods are prepared according to claim 1.
7. a kind of ternary material nickelic according to claim 6 is in lithium ion battery as the application of positive electrode.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101156260A (en) * | 2005-04-15 | 2008-04-02 | 能原材公司 | Cathode active material coated with fluorine compound for lithium secondary batteries and method for preparing the same |
| CN104752700A (en) * | 2013-12-30 | 2015-07-01 | 三星精密化学株式会社 | Cathode active material for lithium secondary battery, method of fabricating the same, and lithium secondary battery including the same |
| CN105070907A (en) * | 2015-08-31 | 2015-11-18 | 宁波金和锂电材料有限公司 | High nickel anode material, preparation method thereof and lithium ion battery |
| US20170179470A1 (en) * | 2015-12-18 | 2017-06-22 | Samsung Electronics Co., Ltd. | Composite positive active material, method of preparing the same, positive electrode including the composite positive active material, and lithium battery including the positive electrode |
| CN107275633A (en) * | 2017-06-13 | 2017-10-20 | 哈尔滨工业大学 | A kind of gradient Fluorin doped tertiary cathode material with low crystal lattice stress and preparation method thereof |
| CN108682845A (en) * | 2018-05-29 | 2018-10-19 | 成都新柯力化工科技有限公司 | A kind of nickelic ternary anode material of lithium battery of surface-stable type and preparation method thereof |
-
2018
- 2018-12-28 CN CN201811624977.5A patent/CN109638279A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101156260A (en) * | 2005-04-15 | 2008-04-02 | 能原材公司 | Cathode active material coated with fluorine compound for lithium secondary batteries and method for preparing the same |
| CN104752700A (en) * | 2013-12-30 | 2015-07-01 | 三星精密化学株式会社 | Cathode active material for lithium secondary battery, method of fabricating the same, and lithium secondary battery including the same |
| CN105070907A (en) * | 2015-08-31 | 2015-11-18 | 宁波金和锂电材料有限公司 | High nickel anode material, preparation method thereof and lithium ion battery |
| US20170179470A1 (en) * | 2015-12-18 | 2017-06-22 | Samsung Electronics Co., Ltd. | Composite positive active material, method of preparing the same, positive electrode including the composite positive active material, and lithium battery including the positive electrode |
| CN107275633A (en) * | 2017-06-13 | 2017-10-20 | 哈尔滨工业大学 | A kind of gradient Fluorin doped tertiary cathode material with low crystal lattice stress and preparation method thereof |
| CN108682845A (en) * | 2018-05-29 | 2018-10-19 | 成都新柯力化工科技有限公司 | A kind of nickelic ternary anode material of lithium battery of surface-stable type and preparation method thereof |
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